Dr. Hari Singh Gour Vishwavidyalaya
Department of Chemistry
M.Sc. IV Semester PURE CHEMISTRY
Course / Title / Credit (s)1.
2.
3.
1.
2.
3.
4.
5.
6.
1.
2
3. / Compulsory
CHE-C-421
CHE-C-422
CHE-C-423
Elective (any two)
CHE-E-424
CHE-E-425
CHE-E-426
CHE-E-427
CHE-E-428
CHE-E-429
CHE-E-4210
Laboratory course
Compulsory
CHE-C-4211
CHE-C-4212
CHE-C-4213 / Spectroscopy, Photochemistry, Solid state Chemistry
Bioinorganic, Bioorganic, Biophysical
Environmental Chemistry
Photo Inorganic chemistry
Organic Synthesis
Medicinal chemistry
Polymers
Chemistry of Supramolecules
Electro Chemistry
Advanced Analytical Chemistry
Laboratory Course in Inorganic Chemistry
Laboratory Course in Organic Chemistry
Laboratory Course in Physical Chemistry / 4
3
2
3
3
3
3
3
3
3
1
1
1
Distribution of marks
Theory courses
Compulsory Papers (CHE-C-421-423)
Elective Papers (CHE-E-424to 429) (Any two)
Compulsory-Laboratory courses: CHE-C-4211, 4212 and 4213
End semester examination will be of 60 marks (2 experiments: 20x2 = 40, Viva=10, Sessional=10.
Practical examination duration will be of 6 hours.
Mid Semester 1 and 2 each of 20 Marks, end semester-60 marks
Compulsory paper- I CHE-C-421
Spectroscopy, Photochemistry and Solid State Chemistry
60 Hrs, Credits-04
Nuclear Magnetic Resonance of Paramagnetic Substances in Solutions
The contact and pseudo-contact shifts, factors affecting nuclear relaxation, some applications including biochemical systems and over view of NMR of metal nuclides with emphasis on Pt195 & Sn 119 NMR.
Moss Bauer Spectroscopy
Basic principles, spectral parameters and spectrum display. Application of the technique to the studies of (1) bonding and structure of Fe2+ and Fe3+ compounds including those of intermediate spin, (2) Sn2+ and Sn4+ compounds – nature of M-L bond, co-ordination number, structure and (3) detection of oxidation states in equivalent MB atoms.
Nuclear Magnetic Resonance Spectroscopy
General introduction and definition, Chemical shift, spin spin interaction, shielding mechanism, mechanism of measurement, chemical shift values and correlation for protons bonded to carbon (aliphatic, olefinic aldehydic and aromatic) and other nuclei (alcohols, phenols, enols, carboxylic acids, amines, amides and mercapto), chemical exchange, effect of deuteration, complex spin – spin interaction between two, three, four and five nuclei ( first order spectra), virtual cpoupling. Stereochemistry, hindered rotation, Karplus curve-variation of coupling constant with dihedral angle. Simplification of complex spectra- nuclear magnetic double resonance, contact shift reagents, solvent effects. Fourier transform technique, nuclear overhauser effect (NOE). Resonance of other nuclei-F, P.
C-13 NMR spectroscopy
General considerations, chemical shift (aliphatic, olefinic, alkyne, aromatic, hetero aromatic and carbonyl carbon), coupling constants.
Two dimension NMR spectroscopy-COSY, NOESY, DEPT, INEPT, APT and INADEQUATE techniques
Photochemistry of Carbonyl Compounds:
Intramolecular reactions of carbonyl compounds – saturated, cyclic and acyclic, b- g unsaturated and a, b - unsaturated compounds. Cyclohexadienones. Intermolecular cycloaddition reactions- dimerisation and oxetane formation
Photochemistry of Aromatic compounds
Isomerisations, additions and substitutions.
Miscellaneous Photochemical Reactions:
Photo- Fries reactions of anillides. Photo-Fries rearrangement. Barion reaction. Single molecular oxygen reactions. Photochemical formation of Smog. Photodegradation of polymers. Photochemistry of vision.
Electronic Properties and Band Theory:
Metals, insulators and semiconductors, electronic structure of solids- band theory, band structure of metals, insulators and semiconductors. Intrinsic and extrinsic semiconductors, doping semiconductors, p-n junctions, super conductors.
Optical properties–Optical reflectance, photo-conduction, photoelectric effects.
Magnetic Properties – Classification of materials: Quantum theory of Paramagnetics-cooperative phenomena-magnetic domains, hysteresius:
Behaviour of substances in a magnetic field, Effect of temperature on magnetic materials, calculation of magnetic moment.
COMPULSORY PAPER – II CHE-C-422
Bio inorganic, Bioorganic and Bio Physical Chemistry 45 Hrs., Credits-03
Bioinorganic Chemistry
Transport and Storage of Dioxygen:-
Heme proteins and oxygen uptake, structure and function of Hemoglobin, Myoglobin, Hemocyanins and Hemerythrin, model synthetic complexes of Iron, cobalt and copper.
Electron Transfer in Biology:-
Structure and function of metalloproteins in electron transport process – cytochromes and Iron – sulpher proteins, synthetic models.
Bio-organic Chemistry:
Kinds of Reactions Catalysed by Enzymes:
Nucleophilic displacement on a phosphorus atom, multiple displacement reactions and the coupling of ATP cleavage to endergonic processes, Transfer of sulphate, addition and elimination reactions, enolic intermediates in isomerization reactios, b - cleavage and condensation, some isomerization and rearrangement reactions, Enzyme catalyzed carboxylation and decarboxylation.
Enzyme Models
Host – guest chemistry, chiral recognition and catalysis, molecular recognition, molecular asymmetry and prochirality. Biomimetic chemistry, crown ether, cryptates.Cyclodextrins, cyclodextrin- based enzyme models, calixarenes, ionophores, micelles, synthetic enzymes or synzymes
Bio-technological applications of enzymes
Large scale production and purification of enzymes, techniques and methods of immobilization of enzymes, effect of immobilization on enzyme activity, application of immobilized enzymes, use of enzymes in food and drink industry- brewing and cheese making, syrups from corn starch, enzymes as targets for drug design. Clinical uses of enzymes, enzyme therapy, enzymes and recombinant DNA technology.
Biophysical Chemistry
Thermodynamics of Biopolymer Solutions
Thermodynamics of biopolymer solutions, osmotics pressure, membrane equilibrium, muscular contraction and energy generation in mechanochemical system.
Cell Membrane and Transport of Ions
Structure and function of cell membrane, ion transport through celll membrane, irreversible thermodynamics treatment of membrane transport, Nerve conduction.
Biopolymers and their Molecular Weights
Evaluation of size, shape molecular weight and extent of hydration of biopolymers by various experimental techniques, Sedimentation equilibrium, hydrodynamic methods, diffusion, sedimentation velocity, viscosity, electrophoresis and rotational motions.
Diffraction Methods
Light scattering, low angle X-Ray scattering, X-Ray diffraction and photo correlation spectroscopy, ORD.
Compulsory Paper – III, CHE–C – 423
Environmental Chemistry
30 Hrs. Credits-02
I. Industrial Pollution
Cement, sugar, distillery, paper and pulp, thermal power plant, nuclear power plant, metallurgy, polymers, drugs, radionuclide analysis, disposal of wastes and their management.
II. Environmental Toxicology
Chemical solutions to environmental problems, biodegradability, principles of decomposition, better industrial processes.
Bhopal gas tragedy, Chernobyl, Three Mile Island and Minamata disasters.
ELECTIVE PAPER
CHE-E-424
Photo inorganic Chemistry
45 Hrs, Credits-03
I. Basis of Photochemistry
Absorption, excitation, photochemical laws, quantum yield, electronically excited states life times-measurements of the times. Flash photolysis, stopped flow techniques. Energy dissipation by radiative and non-radiative processes, absorption spectra, Franck-Condon principle, photochemical stages- primary and secondary processes.
II. Properties of Excited States
Structure, dipole moment, acid-base strengths, reactivity. Photochemical kinetics-calculation of rates of radiative processes. Bimolecular deactivation- quenching.
III. Excited State of Metal Complexes
Excited State of Metal Complexes: comparison with organic compounds, electronically excited states of metal complexes, charge-transfer spectra, charge transfer excitations, methods for obtaining charge-transfer spectra.
IV. Ligand Field Photochemistry
Photo substitution, photo oxidation and photo reduction, lability, and selectivity, zero vibrational levels of ground state and excited state, energy content of excited state, zero-zero spectroscopic energy, development of the equations for redox potentials of the excited states.
V. Redox reactions by Excited Metal Complexes
Energy transfer under conditions of weak interaction and strong interaction-exciplex formation; condition of the excited states to be useful as redox reactants, excited electron transfer, metal complexes as attractive candidates (2,2’-bipyridine and 1,10-phenthroline complexes), illustration of reducing and oxidizing character of Ruthenium2+(bipyridal complexes), comprasion with Fe(bipy)3; role of spin orbital coupling-life time of these complexes, Application of redox processes of electronically excited states for catalytic purposes, transformation of low energy reactants into high energy products, chemical energy into light.
VI. Metal Complexes Sensitizers
Metal complex sensitizer, electrons relay, metal collide systems, and semiconductor supported metal or oxide systems, water photolysis, and nitrogen fixation and carbon dioxide reduction.
Elective Paper
CHE-E 425
Organic Synthesis
45 Hrs, Credits- 03
I. Organometallic Reagents: Principle, preparations, properties and applications of the following in organic synthesis with mechanistic details.
Group I and II metal organic compounds
Li, Mg, Zn and Ce compounds ; Transition metals : Cu, Fe, Rh and Ti compounds. Other elements Si and B.
II. Oxidation : Introduction. Different oxidative processes. Hydrocarbons, Alcohols, Aldehydes, Ketones, Ketals, Amines and Hydrazines. Oxidations with ruthenium tetraoxide, Iodobenzene diacetate and thallium (III) nitrate.
III. Reduction : Introduction. Different reductive processes. Hydrocarbons, Carbonyl compounds Nitro, Nitroso, Azo, Oxime groups and Hydrogenolysis.
IV. Rearrangements
General mechanistic considerations- nature of migration, migratory aptitude, memory effects. A detailed study of the following rearrangements
Pinacol-pinacolone, Wagner-Meerwein, Demjanov, Benzil-Benzilic acid, Favorskii, Arndt-Eistert synthesis, Neber, Beckmann, Hofman, Curtius, Schmidt, Baeyer-Villiger, Shapiro reaction.
V. Metallocenes, Nonbenzenoid Aromatics and Polycyclic Aromatic Compounds General considerations, synthesis and reactions of some representative compounds.
VI. Disconnection Approach
An introduction to synthons and synthetic equivalents, disconnection approach, functional group inter-conversions, one group C-X and two group C-X disconnections, chemoselectivity, reversal of polarity, cyclisation reactions, amine synthesis.
VII Two Group C-C Disconnection: Diels-Alder reaction, α,β-unsaturated carbonyl compounds, Micheal addition and Robinson annelation.
VIII. Ring Synthesis : Saturated heterocycles, synthesis of 3-, 4-, 5- and 6-membered rings, aromatic heterocycles in organic synthesis.
IX. Synthesis of Some Complex Molecules : Application of the above in the synthesis of following compounds:Camphor, Longifoline, Cortisone, Reserpine, Vitamin-D, Juvabione.
Books Suggested
1. Modern Synthetic Reactions, H. O. House, W. A. Benjamin.
2. Some Modern Methods of Organic Synthesis, W. Carruthers, Cambridge Univ. Press.
3. Advanced Organic Chemistry, Reactions Mechanisms and Structure, J. March, John Wiley.
4. Principles of Organic Synthesis, R. O. C. Norman and J. M. Coxon, Blackie Academic and Professional.
5. Advanced Organic Chemistry Part B, F. A. Carey and R. J. Sundberg, Plenum Press.
6. Rodd’s Chemistry of Carbon Compouns, Ed. S. Coffey, Elsevier.
7. Designing Organic Synthesis, S. Warren, Wiley.
8. Organic Synthesis- Concept, Methods and Starting Materials, J. Fuhrhop and G. Penzillin, Verlage VCH.
Elective Paper CHE-E-426
Medicinal Chemistry 45 Hrs, Credits- 03
I. Drug Design
Development of new drugs, procedures followed in drug design, concepts of lead compound and lead modification, concepts of prodrugs and soft drugs, structure-activity relationship (SAR), factors affecting bioactivity, resonance, inductive effect, isosterism, bio-isosterism, spatial considerations. Theories of drug activity: occupancy theory, rate theory, induced fit theory. Quantitative structure activity relationship (QSAR). History and development of QSAR. Concepts of drug receptors. Elementary treatment of drug receptor interactions. Physico-chemical parameters; lipophilicity, partition coefficient, electronic ionization constants, steric, Shelton and surface activity parameters and redox potentials. Free-Wilson analysis, Hansch analysis, relationships between Free-Wilson and Hansch analysis. LD-50, ED-50 (Mathematical derivations of equations excluded).
II. Pharmacokinetics: Introduction to drug absorption, disposition, elimination using pharmacokinetics, important pharmacokinetic parameters in defining drug disposition and in therapeutics. Mention of uses of pharmacokinetics in drug development process.
III. Pharmacodynamics : Introduction, elementary treatment of enzyme stimulation, enzyme inhibition. Sulphonamides, membrane active drugs, drug metabolism, xenobiotics, biotransformation. Significance of drug metabolism in medicinal chemistry.
IV. Antineoplastic Agents : Introdudction, cancer chemotherapy, special problems, role of alkylating agents and antimetabolites in treatment of cancer. Mention of carcinolytic antibiotics and mitotic inhibitors.
Synthesis of mechlorethamine, cyclophosphamide, melphalan, uracil, mustards, and 6-mercaptopurine. Recent development in cancer chemotherapy. Hormone and natural products.
V. Cardiovascular Drugs : Introduction, cardiovascular diseases, drug inhibitors of peripheral sympathetic function. Central intervention of cardiovascular output. Direct acting arteriolar dilators.
Synthesis of amyl nitrate, sorbitrate, diltiazem, quinidine, verapamil, methyldopa, atenolol, oxyprenolol.
VI. Local Antiinfective Drugs : Introduction and general mode of action, Synthesis of sulphonamides, furazolidone, nalidixic acid, ciprofloxacin, norfloxacin, dapsone, amino salicylic acid, isoniazid, ethionamide, ethambutal, fluconazole, econozole, Griseofulvin, chloroquin and primaquin.
VII. Psychoactive Drugs- The Chemotherapy of Mind
Introduction, neurotransmitters, CNS depressants, general anesthetics, mode of action of hypnotics, sedatives, anti-anxiety drugs, benzodiazepines, buspirone, neurochemistry of mental diseases. Antipsychotic drugs- the neuroleptics, antidepressants, butyrophenones, serendipity and drug development, stereochemical aspects of psychotropic drugs. Synthesis of diazepam, oxazepam, chlorazepam, alprazolam, phenytoin, ethosuximde, trimethadione, barbiturates, thiopental sodium, glutethimide.
VIII. Antibiotics
Cell wall biosynthesis, inhibitors, β-lactam rings, antibiotics inhibiting protein synthesis, Synthesis of penicillin-G, penicillin-V, ampicillin, amoxycillin, chloramphenicol, cephalosporin, tetracycline and streptomycin.
1. Introduction to Medicinal Chemistry, A. Gringuage, Wiley-VCH.
2. Wilson and Gisvold’s Text Book of organic Medicinal and Pharmaceutical Chemistry, Ed Robert F. Dorge.
3. An Introduction to Drug Design, S. S. Pandeya and J. R. Dimmock, New Age International.
4. Burger’s Medicinal Chemistry and Drug Discovery, Vol. 1 (Chapter-9 and Ch-14), Ed. M. E. Wolff, John Wiley.
5. Goodman and Gilman’s Pharmacological Basis of Therapeutics, Mc Graw-Hill.
6. The Organic Chemistry of Drug Design and Drug Action, R. B. Silverman, Academic Press.
7. Strategies for Organic Drug Synthesis and Design, D. Lednicer, John Wiley.
MSc Semester IV
CHE-E-427
Polymers
45 Hrs, Credits-03
I Basics
Importance of polymers. Basic concepts: Monomers, repeat units, degree of polymerization. Linear, branched and network polymers. Classification of polymers. Polymerization: condensation, addition, radical chain-ionic and co-ordination and co-polymerization. Polymerization conditions and polymer reactions. Polymerization in homogenous and heterogeneous systems.
II Polymer Characterization
Polydispersion-average molecular weight concept. Number, weight and viscosity average molecular weights. Polydispersity and molecular weight distributions. The practical significance of molecular weight. Measurement of molecular weights. End-group, viscosity, light scattering. Osmotic and ultracentrifugation methods. Analysis and testing of polymers. Chemical analysis of polymers, spectroscopic methods, X-ray diffraction study. Microscopy. Thermal analysis and physical testing-tensile strength. Fatigue, impact. Tear resistance. Hardness and abrasion resistance.
III Structure and Properties
Morphology and order in crystalline polymers-configurations of polymer chains. Crystal structures of polymers. Morphology of crystalline polymers, strain-induced morphology, crystallization and melting. Polymer structure and physical properties-crystalline melting point Tm-melting points of homogenous series, effect of chain flexibility and other steric factors, entropy and heat of fusion. The glass transition temperature Tg, Relationship between Tm and Tg, effect of molecular weight, diluents, chemical structure, chain topology, branching and cross linking. Property requirements and polymer utilization.
IV Polymer Processing
Plastics, elastomers and fibers. Compounding. Processing techniques: Calendaring, die casting, rotational casting, film casting, injection moulding, blow moulding, extrusion moulding, thermoforming, foaming, reinforcing and fibre spinning.
V Properties of Commercial Polymers
Polythene, polyvinyl chloride, polyamides, polyesters, phenolic resins, epoxy resins and silicone polymers. Functional polymers-Fire retarding polymers and electrically conducting polymers. Biomedical polymers-contact lens, dental polymers, artificial heart, kidney, skin and blood cells.
Books Suggested
1. Textbook of Polymer Sciences, F. W. Billmeyer Jr, Wiley.
2. Polymer Sciences, V. R. Gwariker, N. V. Vishwanathan and J. Sreedhar, Willey- Eastern.
3. Functional Monomers and Polymers, K. Takemoto, Y. Inaki and R. M. Ottanbrite.
4. Contemperary Polymer Chemistry, H. R. Alcock and F. W. Lambe, Prentice Hall.
5. Physics and Chemistry of Polymers, J. M. G. Cowie, Blackie Academic and Professional.
Elective Paper –CHE-E-428
Physical Chemistry of Supramolecules
60 hours, Credits-03